US4016145A - Production of aromatic sulfide/sulfone polymers - Google Patents
Production of aromatic sulfide/sulfone polymers Download PDFInfo
- Publication number
- US4016145A US4016145A US05/616,094 US61609475A US4016145A US 4016145 A US4016145 A US 4016145A US 61609475 A US61609475 A US 61609475A US 4016145 A US4016145 A US 4016145A
- Authority
- US
- United States
- Prior art keywords
- sulfide
- sulfone
- carbon atoms
- process according
- alkali metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 60
- 150000003457 sulfones Chemical class 0.000 title claims abstract description 50
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 22
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- -1 aromatic sulfone Chemical class 0.000 claims abstract description 41
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 24
- 229910052977 alkali metal sulfide Inorganic materials 0.000 claims abstract description 17
- 150000003857 carboxamides Chemical class 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims description 42
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 34
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 27
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 11
- 230000018044 dehydration Effects 0.000 claims description 10
- 238000006297 dehydration reaction Methods 0.000 claims description 10
- IAQLJCYTGRMXMA-UHFFFAOYSA-M lithium;acetate;dihydrate Chemical compound [Li+].O.O.CC([O-])=O IAQLJCYTGRMXMA-UHFFFAOYSA-M 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- 230000001747 exhibiting effect Effects 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 239000000460 chlorine Chemical group 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 229940031993 lithium benzoate Drugs 0.000 claims description 5
- LDJNSLOKTFFLSL-UHFFFAOYSA-M lithium;benzoate Chemical compound [Li+].[O-]C(=O)C1=CC=CC=C1 LDJNSLOKTFFLSL-UHFFFAOYSA-M 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- QTNDMWXOEPGHBT-UHFFFAOYSA-N dicesium;sulfide Chemical compound [S-2].[Cs+].[Cs+] QTNDMWXOEPGHBT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052740 iodine Chemical group 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 4
- AHKSSQDILPRNLA-UHFFFAOYSA-N rubidium(1+);sulfide Chemical compound [S-2].[Rb+].[Rb+] AHKSSQDILPRNLA-UHFFFAOYSA-N 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 239000011630 iodine Chemical group 0.000 claims description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 2
- 239000011874 heated mixture Substances 0.000 claims description 2
- 101150108015 STR6 gene Proteins 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 3
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- XWUCFAJNVTZRLE-UHFFFAOYSA-N 7-thiabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound C1=C(S2)C=CC2=C1 XWUCFAJNVTZRLE-UHFFFAOYSA-N 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 238000003556 assay Methods 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- IHYNKGRWCDKNEG-UHFFFAOYSA-N n-(4-bromophenyl)-2,6-dihydroxybenzamide Chemical compound OC1=CC=CC(O)=C1C(=O)NC1=CC=C(Br)C=C1 IHYNKGRWCDKNEG-UHFFFAOYSA-N 0.000 description 8
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 7
- 235000019345 sodium thiosulphate Nutrition 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000001746 injection moulding Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000010128 melt processing Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000012815 thermoplastic material Substances 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- CZGCRRJTGOPIMW-UHFFFAOYSA-N 1,4-bis[(4-chlorophenyl)sulfonyl]benzene Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(S(=O)(=O)C=2C=CC(Cl)=CC=2)C=C1 CZGCRRJTGOPIMW-UHFFFAOYSA-N 0.000 description 1
- UGMPHUWLSLSAHB-UHFFFAOYSA-N 1-(4-bromophenyl)sulfonyl-4-chlorobenzene Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Br)C=C1 UGMPHUWLSLSAHB-UHFFFAOYSA-N 0.000 description 1
- OITNUUJPYBLQSV-UHFFFAOYSA-N 1-(4-chlorophenyl)sulfonyl-4-[4-(4-chlorophenyl)sulfonylphenyl]sulfanylbenzene Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C(C=C1)=CC=C1SC1=CC=C(S(=O)(=O)C=2C=CC(Cl)=CC=2)C=C1 OITNUUJPYBLQSV-UHFFFAOYSA-N 0.000 description 1
- IGDYFOQZXDPWGG-UHFFFAOYSA-N 1-(4-chlorophenyl)sulfonyl-4-[4-(4-chlorophenyl)sulfonylphenyl]sulfonylbenzene Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(S(=O)(=O)C=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(Cl)=CC=2)C=C1 IGDYFOQZXDPWGG-UHFFFAOYSA-N 0.000 description 1
- YWFJOUWACZEICL-UHFFFAOYSA-N 1-(4-chlorophenyl)sulfonyl-4-[5-[4-(4-chlorophenyl)sulfonyl-3-ethylphenyl]nonan-5-yl]-2-ethylbenzene Chemical compound C=1C=C(S(=O)(=O)C=2C=CC(Cl)=CC=2)C(CC)=CC=1C(CCCC)(CCCC)C(C=C1CC)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 YWFJOUWACZEICL-UHFFFAOYSA-N 0.000 description 1
- AZAMPMUEKXNYFW-UHFFFAOYSA-N 1-[2-(2-oxopyrrolidin-1-yl)ethyl]pyrrolidin-2-one Chemical compound O=C1CCCN1CCN1C(=O)CCC1 AZAMPMUEKXNYFW-UHFFFAOYSA-N 0.000 description 1
- USGGGVTXACSIAE-UHFFFAOYSA-N 1-bromo-2-butyl-4-[4-chloro-2-(2-methylpropyl)phenyl]sulfonylbenzene Chemical compound C1=C(Br)C(CCCC)=CC(S(=O)(=O)C=2C(=CC(Cl)=CC=2)CC(C)C)=C1 USGGGVTXACSIAE-UHFFFAOYSA-N 0.000 description 1
- KBBHUNIXDJPEOC-UHFFFAOYSA-N 1-bromo-4-(4-bromo-2,5-diethylphenyl)sulfonyl-2,5-diethylbenzene Chemical compound C1=C(Br)C(CC)=CC(S(=O)(=O)C=2C(=CC(Br)=C(CC)C=2)CC)=C1CC KBBHUNIXDJPEOC-UHFFFAOYSA-N 0.000 description 1
- QBNABJXQGRVIRA-UHFFFAOYSA-N 1-bromo-4-(4-bromophenyl)sulfonylbenzene Chemical compound C1=CC(Br)=CC=C1S(=O)(=O)C1=CC=C(Br)C=C1 QBNABJXQGRVIRA-UHFFFAOYSA-N 0.000 description 1
- RVSRCJINJXHUFY-UHFFFAOYSA-N 1-chloro-4-(4-chloro-2,3,5,6-tetramethylphenyl)sulfonyl-2,3,5,6-tetramethylbenzene Chemical compound CC1=C(Cl)C(C)=C(C)C(S(=O)(=O)C=2C(=C(C)C(Cl)=C(C)C=2C)C)=C1C RVSRCJINJXHUFY-UHFFFAOYSA-N 0.000 description 1
- QYWWZCGTRUQJJF-UHFFFAOYSA-N 1-chloro-4-(4-chloro-2,5-dipropylphenyl)sulfonyl-2,5-dipropylbenzene Chemical compound C1=C(Cl)C(CCC)=CC(S(=O)(=O)C=2C(=CC(Cl)=C(CCC)C=2)CCC)=C1CCC QYWWZCGTRUQJJF-UHFFFAOYSA-N 0.000 description 1
- PLVUIVUKKJTSDM-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)sulfonylbenzene Chemical compound C1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(F)C=C1 PLVUIVUKKJTSDM-UHFFFAOYSA-N 0.000 description 1
- AVGQIRXZUNRSAY-UHFFFAOYSA-N 1-iodo-4-(4-iodophenyl)sulfonylbenzene Chemical compound C1=CC(I)=CC=C1S(=O)(=O)C1=CC=C(I)C=C1 AVGQIRXZUNRSAY-UHFFFAOYSA-N 0.000 description 1
- UFYBAHZTNKXBNX-UHFFFAOYSA-N 2,4-bis[(4-fluorophenyl)sulfonyl]-1-methylbenzene Chemical compound CC1=CC=C(S(=O)(=O)C=2C=CC(F)=CC=2)C=C1S(=O)(=O)C1=CC=C(F)C=C1 UFYBAHZTNKXBNX-UHFFFAOYSA-N 0.000 description 1
- GFCRTPHXRNJSAO-UHFFFAOYSA-N 2,6-bis[(4-bromophenyl)sulfonyl]naphthalene Chemical compound C1=CC(Br)=CC=C1S(=O)(=O)C1=CC=C(C=C(C=C2)S(=O)(=O)C=3C=CC(Br)=CC=3)C2=C1 GFCRTPHXRNJSAO-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- OXVRRLTWCAROJB-UHFFFAOYSA-N 2-butyl-1-(2-butyl-4-fluorophenyl)sulfonyl-4-fluorobenzene Chemical compound CCCCC1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(F)C=C1CCCC OXVRRLTWCAROJB-UHFFFAOYSA-N 0.000 description 1
- FGQIBZIWKLWOHF-UHFFFAOYSA-N 3-ethyl-1,5-bis[(4-iodophenyl)sulfonyl]naphthalene Chemical compound C12=CC(CC)=CC(S(=O)(=O)C=3C=CC(I)=CC=3)=C2C=CC=C1S(=O)(=O)C1=CC=C(I)C=C1 FGQIBZIWKLWOHF-UHFFFAOYSA-N 0.000 description 1
- DZXRPCNJQDADRH-UHFFFAOYSA-N 4-chloro-1-(4-chloro-2-methylphenyl)sulfonyl-2-methylbenzene Chemical compound CC1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1C DZXRPCNJQDADRH-UHFFFAOYSA-N 0.000 description 1
- OIRBZGZDHXBOFW-UHFFFAOYSA-M 4-ethyltetradecanoate;rubidium(1+) Chemical compound [Rb+].CCCCCCCCCCC(CC)CCC([O-])=O OIRBZGZDHXBOFW-UHFFFAOYSA-M 0.000 description 1
- 125000006306 4-iodophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1I 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- NEDPBMIBOQZRIS-UHFFFAOYSA-N [Na].S=S Chemical compound [Na].S=S NEDPBMIBOQZRIS-UHFFFAOYSA-N 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- HYWCISCKYCCFMI-UHFFFAOYSA-M butanoate;rubidium(1+) Chemical compound [Rb+].CCCC([O-])=O HYWCISCKYCCFMI-UHFFFAOYSA-M 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- WDPREJLILODKKB-UHFFFAOYSA-M cesium;cyclododecanecarboxylate Chemical compound [Cs+].[O-]C(=O)C1CCCCCCCCCCC1 WDPREJLILODKKB-UHFFFAOYSA-M 0.000 description 1
- NMKVMUXQLXZRNQ-UHFFFAOYSA-M cesium;hexanoate Chemical compound [Cs+].CCCCCC([O-])=O NMKVMUXQLXZRNQ-UHFFFAOYSA-M 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- CKDDRHZIAZRDBW-UHFFFAOYSA-N henicosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCC(O)=O CKDDRHZIAZRDBW-UHFFFAOYSA-N 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- IFXWSHQRYWTGOH-UHFFFAOYSA-M lithium;2-(4-ethylcyclohexyl)acetate Chemical compound [Li+].CCC1CCC(CC([O-])=O)CC1 IFXWSHQRYWTGOH-UHFFFAOYSA-M 0.000 description 1
- CHGXQXZWZFRAOH-UHFFFAOYSA-M lithium;2-methyloctanoate Chemical compound [Li+].CCCCCCC(C)C([O-])=O CHGXQXZWZFRAOH-UHFFFAOYSA-M 0.000 description 1
- IIDVGIFOWJJSIJ-UHFFFAOYSA-M lithium;2-methylpropanoate Chemical compound [Li+].CC(C)C([O-])=O IIDVGIFOWJJSIJ-UHFFFAOYSA-M 0.000 description 1
- ZSICDRPAYOOLQB-UHFFFAOYSA-M lithium;2-phenylacetate Chemical compound [Li+].[O-]C(=O)CC1=CC=CC=C1 ZSICDRPAYOOLQB-UHFFFAOYSA-M 0.000 description 1
- OYTJIZNGQNUSAK-UHFFFAOYSA-M lithium;cyclohexanecarboxylate Chemical compound [Li+].[O-]C(=O)C1CCCCC1 OYTJIZNGQNUSAK-UHFFFAOYSA-M 0.000 description 1
- RQZHWDLISAJCLK-UHFFFAOYSA-M lithium;heptanoate Chemical compound [Li+].CCCCCCC([O-])=O RQZHWDLISAJCLK-UHFFFAOYSA-M 0.000 description 1
- KDDRURKXNGXKGE-UHFFFAOYSA-M lithium;pentanoate Chemical compound [Li+].CCCCC([O-])=O KDDRURKXNGXKGE-UHFFFAOYSA-M 0.000 description 1
- AXMOZGKEVIBBCF-UHFFFAOYSA-M lithium;propanoate Chemical compound [Li+].CCC([O-])=O AXMOZGKEVIBBCF-UHFFFAOYSA-M 0.000 description 1
- GPSDUZXPYCFOSQ-UHFFFAOYSA-M m-toluate Chemical compound CC1=CC=CC(C([O-])=O)=C1 GPSDUZXPYCFOSQ-UHFFFAOYSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KAONDSIEAGDWKS-UHFFFAOYSA-N n,n-dipropylbutanamide Chemical compound CCCN(CCC)C(=O)CCC KAONDSIEAGDWKS-UHFFFAOYSA-N 0.000 description 1
- ABMDIECEEGFXNC-UHFFFAOYSA-N n-ethylpropanamide Chemical compound CCNC(=O)CC ABMDIECEEGFXNC-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000004300 potassium benzoate Substances 0.000 description 1
- 235000010235 potassium benzoate Nutrition 0.000 description 1
- 229940103091 potassium benzoate Drugs 0.000 description 1
- FDJJMQRIEWTAQS-UHFFFAOYSA-M potassium;2-(4-methylphenyl)acetate Chemical compound [K+].CC1=CC=C(CC([O-])=O)C=C1 FDJJMQRIEWTAQS-UHFFFAOYSA-M 0.000 description 1
- HLCXPTFJMZUPPP-UHFFFAOYSA-M potassium;2-cyclohexylacetate Chemical compound [K+].[O-]C(=O)CC1CCCCC1 HLCXPTFJMZUPPP-UHFFFAOYSA-M 0.000 description 1
- HIDKSOTTZRMUML-UHFFFAOYSA-M potassium;dodecanoate Chemical compound [K+].CCCCCCCCCCCC([O-])=O HIDKSOTTZRMUML-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 229960003885 sodium benzoate Drugs 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 1
- 239000004324 sodium propionate Substances 0.000 description 1
- 235000010334 sodium propionate Nutrition 0.000 description 1
- 229960003212 sodium propionate Drugs 0.000 description 1
- ZZYMZNLESRCHHY-UHFFFAOYSA-M sodium;3-methylcyclopentane-1-carboxylate Chemical compound [Na+].CC1CCC(C([O-])=O)C1 ZZYMZNLESRCHHY-UHFFFAOYSA-M 0.000 description 1
- KDGFSUSPVCYLFX-UHFFFAOYSA-M sodium;4-phenylcyclohexane-1-carboxylate Chemical compound [Na+].C1CC(C(=O)[O-])CCC1C1=CC=CC=C1 KDGFSUSPVCYLFX-UHFFFAOYSA-M 0.000 description 1
- LHYPLJGBYPAQAK-UHFFFAOYSA-M sodium;pentanoate Chemical compound [Na+].CCCCC([O-])=O LHYPLJGBYPAQAK-UHFFFAOYSA-M 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0236—Polyarylenethioethers containing atoms other than carbon or sulfur in a linkage between arylene groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/025—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/025—Preparatory processes
- C08G75/0254—Preparatory processes using metal sulfides
Definitions
- This invention relates to the production of polymers from aromatic compounds.
- this invention relates to a process for the production of high molecular weight aromatic sulfide/sulfone polymers by reacting a dihalo aromatic sulfone, a selected alkali metal sulfide, and an organic amide in the presence of an alkali metal carboxylate.
- this invention relates to the production of p-phenylene sulfide/sulfone polymers by reacting a bis(p-halophenyl) sulfone, a selected alkali metal sulfide, and an organic amide in the presence of an alkali metal carboxylate.
- thermoplastic materials can be molded rapidly and efficiently into almost any desired shape, they lend themselves to mass production.
- an object of this invention is to produce aromatic sulfide/sulfone polymers exhibiting higher molecular weight than normally obtained.
- Another object of this invention is to provide a process for producing high molecular weight aromatic sulfide/sulfone polymers exhibiting good melt processability properties.
- an aromatic sulfide/sulfone polymer by employing a dihalo aromatic sulfone, an alkali metal sulfide other than lithium sulfide, and an organic amide, the use, additionally, of an alkali metal carboxylate results in an aromatic sulfide/sulfone polymer of higher molecular weight, as evidenced by a higher inherent viscosity, than that obtained without the use of the alkali metal carboxylate.
- At least one dihalo aromatic sulfone such as a bis(p-halophenyl) sulfone, at least one alkali metal sulfide selected from the group consisting of sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide, at least one alkali metal carboxylate, and at least one organic amide are contacted under polymerization conditions for a period of time sufficient to form an aromatic sulfide/sulfone polymer.
- a dihalo aromatic sulfone such as a bis(p-halophenyl) sulfone
- at least one alkali metal sulfide selected from the group consisting of sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide
- at least one alkali metal carboxylate selected from the group consisting of sodium sulfide, potassium sulfide, rubidium
- At least one dihalo aromatic sulfone is reacted, under polymerization conditions for a period of time sufficient to form an aromatic sulfide/sulfone polymer, with a mixture in which at least one alkali metal sulfide other than lithium sulfide, at least one alkali metal carboxylate, and at least one organic amide are contacted.
- Dihalo aromatic sulfones that can be employed in the process of the invention have the formula ##STR1## where each X is selected from the group consisting of fluorine, chlorine, bromine, and iodine; Z is a divalent radical selected from the group consisting of ##STR2## n is 0 or 1; A is selected from the group consisting of oxygen, sulfur, sulfonyl, and CR 2 ; and each R is selected from the group consisting of hydrogen and alkyl radicals having 1 to about 4 carbon atoms, the total number of carbon atoms in all of the R groups in the molecule being 0 to about 12.
- each n is 0.
- Bis(p-halophenyl) sulfones are presently preferred reactants in the process of this invention and can be represented by the formula ##STR3## where each X is selected from the group consisting of fluorine, chorine, bromine, and iodine, and each R is selected from the group consisting of hydrogen and alkyl radicals having 1 to about 4 carbon atoms, the total number of carbon atoms in each molecule being within the range of 12 to about 24.
- dihalo aromatic sulfones examples include bis(p-fluorophenyl) sulfone, bis(p-chlorophenyl) sulfone, bis(p-bromophenyl) sulfone, bis(p-iodophenyl) sulfone, p-chlorophenyl p-bromophenyl sulfone, p-iodophenyl 3-methy-4-fluorophenyl sulfone, bis(2-methyl-4-chlorophenyl) sulfone, bis(2,5-diethyl-4-bromophenyl) sulfone, bis(3-iospropyl-4-iodophenyl) sulfone, bis(2,5-dipropyl-4-chloro-phenyl) sulfone, bis(2-butyl-4-fluorophenyl)
- Alkali metal sulfides that can be employed in the process of this invention include sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and mixtures thereof.
- the alkali metal sulfide can be used in anhydrous form, as a hydrate, or as an aqueous mixture.
- Alkali metal carboxylates that can be employed in the process of this invention can be represented by the formula R'CO 2 M where R' is a hydrocarbyl radical selected from alkyl, cycloalkyl, and aryl, and combinations thereof such as alkaryl, aralkyl, and the like, the number of carbon atoms in said R' being within the range of 1 to about 20, and M is an alkali metal selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium.
- R' is an alkyl radical having 1 to about 6 carbon atoms or a phenyl radical and M is lithium.
- the alkali metal carboxylate can be employed as a hydrate or as a solution or dispersion in water.
- alkali metal carboxylates examples include lithium acetate, sodium acetate, potassium acetate, lithium propionate, sodium propionate, lithium 2-methylpropionate, rubidium butyrate, lithium valerate, sodium valerate, cesium hexanoate, lithium heptanoate, lithium 2-methyloctanoate, potassium dodecanoate, rubidium 4-ethyltetradecanoate, sodium octadecanoate, sodium heneicosanoate, lithium cyclohexanecarboxylate, cesium cyclododecanecarboxylate, sodium 3-methylcyclopentanecarboxylate, potassium cyclohexylacetate, potassium benzoate, lithium benzoate, sodium benzoate, potassium m-toluate, lithium phenylacetate, sodium 4-phenylcyclohexanecarboxylate, potassium p-tolylacetate, lithium 4-ethylcyclohe
- the organic amides used in the method of this invention should be substantially liquid at the reaction temperatures and pressures employed.
- the amides can be cyclic or acyclic and can have 1 to about 10 carbon atoms per molecule.
- suitable amides include formamide, acetamide, N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-ethylpropionamide, N,N-dipropylbutyramide, 2-pyrrolidone, N-methyl-2-pyrrolidone, ⁇ -caprolactam, N-methyl- ⁇ -caprolactam, N,N'-ethylenedi-2-pyrrolidone, hexamethylphosphoramide, tetramethylurea, and the like, and mixtures thereof.
- aromatic sulfide/sulfone polymers produced by the process of this invention can be characterized as having recurring ##STR4## units, where each R, Z, and n is as defined above.
- reaction conditions can be employed in the practice of the invention.
- the reaction conditions under which the reactions involved in the invention will take place are within the scope of the invention.
- any proportions of reactants which will react with each other to produce a product polymer of the invention are within the scope of the invention.
- certain reaction conditions and reactant proportions are favored for economic reasons, i.e., the reactions proceed faster and give greater yields for some reaction conditions and some proportions of reactants.
- the mole ratio of dihalo aromatic sulfone to alkali metal sulfide can vary over a considerable range, generally it will be within the range of about 0.9:1 to about 2:1, preferably about 0.95:1 to about 1.2:1.
- a mole ratio of dihalo aromatic sulfone to alkali metal sulfide within the range of about 1:1 to about 1.03:1 is preferred.
- the mole ratio of alkali metal carboxylate to alkali metal sulfide can vary over a wide range but generally will be within the range of about 0.05:1 to about 4:1, preferably about 0.1:1 to about 2:1.
- the amount of organic amide can vary greatly, generally being within the range of about 100 grams to about 2500 grams per gram-mole of alkali metal sulfide.
- reaction temperature at which the polymerization is conducted can vary over a considerable range, generally it will be within the range of about 170° C to about 240° C, preferably about 180° C to about 220° C.
- the reaction time can vary widely, depending in part on the reaction temperature, but generally will be within the range of about 10 minutes to about 3 days, preferably about 1 hour to about 8 hours.
- the pressure should be sufficient to maintain the dihalo aromatic sulfone and organic amide substantially in the liquid phase.
- the process of this invention can be carried out by mixing the dihalo aromatic sulfone, the alkali metal sulfide, the alkali metal carboxylate, and the organic amide in any order. It is also to be understood that a composite can be formed of any two or more of these substances with the remaining substance or substances being introduced into the composite. Furthermore, it is to be understood that these substances can be employed in the form of aqueous mixtures or hydrates and that subsequent to any step of contacting substances, water can be removed from the resulting composition, e.g., by heating, distilling, and the like.
- water can be removed by distillation from a mixture of the organic amide, the alkali metal carboxylate, e.g., in anhydrous form or as a hydrate, and the alkali metal sulfide in hydrated form or as an aqueous mixture, after which the residual mixture can be admixed with the dihalo aromatic sulfone and the resulting mixture then maintained at polymerization conditions.
- the alkali metal carboxylate e.g., in anhydrous form or as a hydrate
- the alkali metal sulfide in hydrated form or as an aqueous mixture
- the alkali metal sulfide, the alkali metal carboxylate, and the organic amide are combined to form a reactant mixture which is heated at an elevated temperature for a period of time sufficient to effect dehydration of the mixture followed by addition of the dihalo aromatic sulfone to the heated mixture, with or without cooling prior to addition of the sulfone, and then subjecting the resulting reaction mass to polymerization conditions which forms an aromatic sulfide/sulfone polymer.
- the heating can be carried out at a temperature in the range of about 170° C to about 240° C although temperatures of about 200° C to about 210° C have been found satisfactory.
- the sulfone is ordinarily added to the reactant mixture together with organic amide.
- the aromatic sulfide/sulfone polymers produced by the process of this invention can be separated from the reaction mixture by conventional procedures, e.g., by filtration of the polymer, followed by washing with water, or by dilution of the reaction mixture with water, followed by filtration and water washing of the polymer.
- at least a portion of the washing with water is conducted at an elevated temperature, e.g., within the range of about 130° C to about 250° C, preferably about 160° C to about 230° C, to provide a polymer which is low in ash-forming substances and is relatively light in color and of good clarity, as well as exhibiting good melt flow stability under conditions of melt processing operations such as injection molding.
- the aromatic sulfide/sulfone polymers produced by the process of this invention can be blended with fillers, pigments, extenders, other polymers, and the like. They can be cured through crosslinking and/or chain extension, e.g., by heating at temperatures up to about 480° C in the presence of a free oxygen-containing gas, to provide cured products having high thermal stability and good chemical resistance. They are useful in the production of coatings, film, molded objects, and fibers. The polymers exhibit a good balance of properties for these uses, the heat deflection temperature being particularly outstanding.
- values for inherent viscosity were determined at 30° C in a 3:2 mixture, by weight, of phenol and 1,1,2,2-tetrachloroethane at a polymer concentration of 0.5 g/100 ml solution.
- Values for glass transition temperature (T g ) were determined on premelted and quenched polymer samples by differential thermal analysis.
- the values for polymer-melt temperature (PMT) were determined by placing portions of the polymer on a heated bar with a temperature gradient.
- the name poly(p-phenylene sulfide/sulfone) is used to describe an aromatic sulfide/sulfone polymer having recurring ##STR5## units in the polymer molecule.
- the poly(p-phenylene sulfide/sulfone) produced in this Example was of much higher molecular weight than that produced in Example I, in which lithium acetate dihydrate was not employed.
- the poly(p-phenylene sulfide/sulfone) exhibited a good balance of properties, the heat deflection temperature being particularly outstanding.
- the resulting mixture was heated for 5 hours at 200° C at a pressure of 45-55 psig.
- the reaction product was washed repeatedly with hot water and dried at 80° C under nitrogen in a vacuum oven to obtain a yield of 109.5 g of amorphous poly(p-phenylene sulfide/sulfone) having an inherent viscosity of 0.36, a T g of 209° C, and a PMT of 275° C.
- the resulting mixture was heated for 5 hours at 200° C at a pressure of 65-75 psig.
- the reaction product was washed repeatedly with hot water and dried at 80° C under nitrogen in a vacuum oven to obtain a yield of 116.9 g of amorphous poly(p-phenylene sulfide/sulfone) having an inherent viscosity of 0.52, a T.sub. g of 210° C, and a PMT of 275° C.
- the poly(p-phenylene sulfide/sulfone) produced in this Example was of much higher molecular weight than that produced in Example III, in which lithium acetate dihydrate was not employed.
- the poly(p-phenylene sulfide/sulfone) produced in this Example was of much higher molecular weight than that produced in Example V, in which lithium benzoate was not employed.
- the reaction product was washed repeatedly with hot water and dried at 80° C under nitrogen in a vacuum oven to obtain a yield of 122.2 g of amorphous poly(p-phenylene sulfide/sulfone) having an inherent viscosity of 0.37, a T g of 209° C, and a PMT of 275° C.
- the melt flow of this polymer determined by the method of ASTM D 1238-70, modified to a temperature of 316° C using a 5-kg weight, was 8 g/10 min.
- the cooled reaction product was washed eight times with hot (approximately 80° C) water. A minor portion of this washed product was dried at 80° C under nitrogen in a vacuum oven to obtain 17.4 g of amorphous poly(p-phenylene sulfide/sulfone) (Polymer A). The remainder of the washed product was subjected to further washing by stirring in an autoclave with 400 ml water at 200° C for 1 hour. The mixture was cooled and filtered, and the polymer was again washed by stirring in an autoclave with 400 ml water at 200° C for 1 hour.
- Polymer B amorphous poly(p-phenylene sulfide/sulfone)
- Polymer B which had been washed with water at 200° C, gave a much lower value for ash than did Polymer A, which was washed only at the lower temperature. Also, Polymer B exhibited much greater melt flow stability under conditions of the melt flow test, a characteristic desirable in melt processing operations such as injection molding.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
High molecular weight aromatic sulfide/sulfone polymers are produced by reacting a dihalo aromatic sulfone, an alkali metal sulfide other than lithium sulfide, an organic amide, and an alkali metal carboxylate. Use of the alkali metal carboxylate results in polymers of high molecular weight and satisfactory melt flow properties having utility as coatings, films, molded objects, fibers, and the like.
Description
This application is a continuation-in-part application of my copending application having Ser. No. 495,450, filed Aug. 28, 1974, now U.S. Pat. No. 3,919,177, issued Nov. 11, 1975, which is a continuation-in-part application of Ser. No. 416,776, filed Nov. 19, 1973, now abandoned.
This invention relates to the production of polymers from aromatic compounds. In accordance with another aspect, this invention relates to a process for the production of high molecular weight aromatic sulfide/sulfone polymers by reacting a dihalo aromatic sulfone, a selected alkali metal sulfide, and an organic amide in the presence of an alkali metal carboxylate. In accordance with a further aspect, this invention relates to the production of p-phenylene sulfide/sulfone polymers by reacting a bis(p-halophenyl) sulfone, a selected alkali metal sulfide, and an organic amide in the presence of an alkali metal carboxylate.
In recent years, a wide variety of high polymers have been prepared, many of which are currently being produced and marketed on a large scale. While such polymers are useful in many areas, one property of high polymers, particularly those of the thermoplastic type, which needs to be improved is ability to withstand high temperature. Since thermoplastic materials can be molded rapidly and efficiently into almost any desired shape, they lend themselves to mass production. The high polymer, especially a thermoplastic material, which could stand very high temperatures and thus could be used in such areas as electrical components, wire coatings, automotive parts, and the like, has been the objective of a great deal of research.
Accordingly, an object of this invention is to produce aromatic sulfide/sulfone polymers exhibiting higher molecular weight than normally obtained.
Another object of this invention is to provide a process for producing high molecular weight aromatic sulfide/sulfone polymers exhibiting good melt processability properties.
It is another object of this invention to provide a method employing a specific type of compound for the preparation of aromatic sulfide/sulfone polymers of increased molecular weight suitable for injection molding.
Other objects and aspects as well as the several advantages of this invention are apparent from a study of this disclosure and the appended claims.
In accordance with this invention, in the production of an aromatic sulfide/sulfone polymer by employing a dihalo aromatic sulfone, an alkali metal sulfide other than lithium sulfide, and an organic amide, the use, additionally, of an alkali metal carboxylate results in an aromatic sulfide/sulfone polymer of higher molecular weight, as evidenced by a higher inherent viscosity, than that obtained without the use of the alkali metal carboxylate.
In one embodiment of the present invention, at least one dihalo aromatic sulfone such as a bis(p-halophenyl) sulfone, at least one alkali metal sulfide selected from the group consisting of sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide, at least one alkali metal carboxylate, and at least one organic amide are contacted under polymerization conditions for a period of time sufficient to form an aromatic sulfide/sulfone polymer.
In another embodiment of this invention, at least one dihalo aromatic sulfone is reacted, under polymerization conditions for a period of time sufficient to form an aromatic sulfide/sulfone polymer, with a mixture in which at least one alkali metal sulfide other than lithium sulfide, at least one alkali metal carboxylate, and at least one organic amide are contacted.
Dihalo aromatic sulfones that can be employed in the process of the invention have the formula ##STR1## where each X is selected from the group consisting of fluorine, chlorine, bromine, and iodine; Z is a divalent radical selected from the group consisting of ##STR2## n is 0 or 1; A is selected from the group consisting of oxygen, sulfur, sulfonyl, and CR2 ; and each R is selected from the group consisting of hydrogen and alkyl radicals having 1 to about 4 carbon atoms, the total number of carbon atoms in all of the R groups in the molecule being 0 to about 12. Preferably, each n is 0.
Bis(p-halophenyl) sulfones are presently preferred reactants in the process of this invention and can be represented by the formula ##STR3## where each X is selected from the group consisting of fluorine, chorine, bromine, and iodine, and each R is selected from the group consisting of hydrogen and alkyl radicals having 1 to about 4 carbon atoms, the total number of carbon atoms in each molecule being within the range of 12 to about 24.
Examples of some dihalo aromatic sulfones that can be employed in the process of this invention include bis(p-fluorophenyl) sulfone, bis(p-chlorophenyl) sulfone, bis(p-bromophenyl) sulfone, bis(p-iodophenyl) sulfone, p-chlorophenyl p-bromophenyl sulfone, p-iodophenyl 3-methy-4-fluorophenyl sulfone, bis(2-methyl-4-chlorophenyl) sulfone, bis(2,5-diethyl-4-bromophenyl) sulfone, bis(3-iospropyl-4-iodophenyl) sulfone, bis(2,5-dipropyl-4-chloro-phenyl) sulfone, bis(2-butyl-4-fluorophenyl) sulfone, bis(2,3,5,6-tetramethyl-4-chlorophenyl) sulfone, 2-isobutyl-4-chlorophenyl 3-butyl-4-bromophenyl sulfone, 1,4-bis(p-chlorophenylsulfonyl)benzene, 1-methyl-2,4-bis(p-fluorophenylsulfonyl)benzene, 2,6-bis(p-bromophenylsulfonyl)naphthalene, 7-ethyl-1,5-bis(p-iodophenylsulfonyl)naphthalene, 4,4'-bis(p-chlorophenylsulfonyl)biphenyl,bis[p-(p-bromophenylsulfonyl)phenyl] ether, bis[p-(p-chlorophenylsulfonyl)phenyl] sulfide, bis[p-(p-chlorophenylsulfonyl)phenyl] sulfone, bis-[p-(p-bromophenylsufonyl)phenyl]methane, 5,5-bis[3-ethyl-4-(p-chlorophenylsulfonyl)phenyl]nonane, and the like, and mixtures thereof.
Alkali metal sulfides that can be employed in the process of this invention include sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and mixtures thereof. The alkali metal sulfide can be used in anhydrous form, as a hydrate, or as an aqueous mixture.
Alkali metal carboxylates that can be employed in the process of this invention can be represented by the formula R'CO2 M where R' is a hydrocarbyl radical selected from alkyl, cycloalkyl, and aryl, and combinations thereof such as alkaryl, aralkyl, and the like, the number of carbon atoms in said R' being within the range of 1 to about 20, and M is an alkali metal selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium. Preferably, R' is an alkyl radical having 1 to about 6 carbon atoms or a phenyl radical and M is lithium. If desired, the alkali metal carboxylate can be employed as a hydrate or as a solution or dispersion in water.
Examples of some alkali metal carboxylates that can be employed in the process of this invention include lithium acetate, sodium acetate, potassium acetate, lithium propionate, sodium propionate, lithium 2-methylpropionate, rubidium butyrate, lithium valerate, sodium valerate, cesium hexanoate, lithium heptanoate, lithium 2-methyloctanoate, potassium dodecanoate, rubidium 4-ethyltetradecanoate, sodium octadecanoate, sodium heneicosanoate, lithium cyclohexanecarboxylate, cesium cyclododecanecarboxylate, sodium 3-methylcyclopentanecarboxylate, potassium cyclohexylacetate, potassium benzoate, lithium benzoate, sodium benzoate, potassium m-toluate, lithium phenylacetate, sodium 4-phenylcyclohexanecarboxylate, potassium p-tolylacetate, lithium 4-ethylcyclohexylacetate, and the like, and mixtures thereof.
The organic amides used in the method of this invention should be substantially liquid at the reaction temperatures and pressures employed. The amides can be cyclic or acyclic and can have 1 to about 10 carbon atoms per molecule. Examples of some suitable amides include formamide, acetamide, N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-ethylpropionamide, N,N-dipropylbutyramide, 2-pyrrolidone, N-methyl-2-pyrrolidone, ε-caprolactam, N-methyl-ε-caprolactam, N,N'-ethylenedi-2-pyrrolidone, hexamethylphosphoramide, tetramethylurea, and the like, and mixtures thereof.
The aromatic sulfide/sulfone polymers produced by the process of this invention can be characterized as having recurring ##STR4## units, where each R, Z, and n is as defined above.
A wide variety of reaction conditions can be employed in the practice of the invention. The reaction conditions under which the reactions involved in the invention will take place are within the scope of the invention. Similarly, any proportions of reactants which will react with each other to produce a product polymer of the invention are within the scope of the invention. However, as will be understood by those skilled in the art in view of this disclosure, certain reaction conditions and reactant proportions are favored for economic reasons, i.e., the reactions proceed faster and give greater yields for some reaction conditions and some proportions of reactants.
Although the mole ratio of dihalo aromatic sulfone to alkali metal sulfide can vary over a considerable range, generally it will be within the range of about 0.9:1 to about 2:1, preferably about 0.95:1 to about 1.2:1. When the polymer is to be employed in applications such as injection molding, where good melt processability is desired, a mole ratio of dihalo aromatic sulfone to alkali metal sulfide within the range of about 1:1 to about 1.03:1 is preferred. The mole ratio of alkali metal carboxylate to alkali metal sulfide can vary over a wide range but generally will be within the range of about 0.05:1 to about 4:1, preferably about 0.1:1 to about 2:1. The amount of organic amide can vary greatly, generally being within the range of about 100 grams to about 2500 grams per gram-mole of alkali metal sulfide.
Although the reaction temperature at which the polymerization is conducted can vary over a considerable range, generally it will be within the range of about 170° C to about 240° C, preferably about 180° C to about 220° C. The reaction time can vary widely, depending in part on the reaction temperature, but generally will be within the range of about 10 minutes to about 3 days, preferably about 1 hour to about 8 hours. The pressure should be sufficient to maintain the dihalo aromatic sulfone and organic amide substantially in the liquid phase.
It is to be understood that the process of this invention can be carried out by mixing the dihalo aromatic sulfone, the alkali metal sulfide, the alkali metal carboxylate, and the organic amide in any order. It is also to be understood that a composite can be formed of any two or more of these substances with the remaining substance or substances being introduced into the composite. Furthermore, it is to be understood that these substances can be employed in the form of aqueous mixtures or hydrates and that subsequent to any step of contacting substances, water can be removed from the resulting composition, e.g., by heating, distilling, and the like. For instance, water can be removed by distillation from a mixture of the organic amide, the alkali metal carboxylate, e.g., in anhydrous form or as a hydrate, and the alkali metal sulfide in hydrated form or as an aqueous mixture, after which the residual mixture can be admixed with the dihalo aromatic sulfone and the resulting mixture then maintained at polymerization conditions. In one presently preferred embodiment, the alkali metal sulfide, the alkali metal carboxylate, and the organic amide are combined to form a reactant mixture which is heated at an elevated temperature for a period of time sufficient to effect dehydration of the mixture followed by addition of the dihalo aromatic sulfone to the heated mixture, with or without cooling prior to addition of the sulfone, and then subjecting the resulting reaction mass to polymerization conditions which forms an aromatic sulfide/sulfone polymer. The heating can be carried out at a temperature in the range of about 170° C to about 240° C although temperatures of about 200° C to about 210° C have been found satisfactory. The sulfone is ordinarily added to the reactant mixture together with organic amide.
The aromatic sulfide/sulfone polymers produced by the process of this invention can be separated from the reaction mixture by conventional procedures, e.g., by filtration of the polymer, followed by washing with water, or by dilution of the reaction mixture with water, followed by filtration and water washing of the polymer. Preferably, at least a portion of the washing with water is conducted at an elevated temperature, e.g., within the range of about 130° C to about 250° C, preferably about 160° C to about 230° C, to provide a polymer which is low in ash-forming substances and is relatively light in color and of good clarity, as well as exhibiting good melt flow stability under conditions of melt processing operations such as injection molding.
The aromatic sulfide/sulfone polymers produced by the process of this invention can be blended with fillers, pigments, extenders, other polymers, and the like. They can be cured through crosslinking and/or chain extension, e.g., by heating at temperatures up to about 480° C in the presence of a free oxygen-containing gas, to provide cured products having high thermal stability and good chemical resistance. They are useful in the production of coatings, film, molded objects, and fibers. The polymers exhibit a good balance of properties for these uses, the heat deflection temperature being particularly outstanding.
In the following Examples, values for inherent viscosity were determined at 30° C in a 3:2 mixture, by weight, of phenol and 1,1,2,2-tetrachloroethane at a polymer concentration of 0.5 g/100 ml solution. Values for glass transition temperature (Tg) were determined on premelted and quenched polymer samples by differential thermal analysis. The values for polymer-melt temperature (PMT) were determined by placing portions of the polymer on a heated bar with a temperature gradient. The name poly(p-phenylene sulfide/sulfone) is used to describe an aromatic sulfide/sulfone polymer having recurring ##STR5## units in the polymer molecule.
In a control run outside the scope of this invention, 65.2 g (60 percent assay, 0.5 mole) sodium sulfide, 0.2 g sodium hydroxide (to react with sodium bisulfide and sodium thiosulfide present in trace amounts in the sodium sulfide), and 158.3 g N-methyl-2-pyrrolidone were charged to a stirred 1-liter autoclave, which was then flushed with nitrogen. Dehydration of the mixture by heating to 205° C yielded 19 ml of distillate containing 18.2 g water. To the residual mixture were charged 143.6 g (0.5 mole) bis(p-chlorophenyl) sulfone (melting point, 146°-147° C) and 40 g N-methyl-2-pyrrolidone. The resulting mixture was heated for 5 hours at 200° C at a pressure of 40-45 psig. The reaction product was washed repeatedly with hot water and dried at 80° C under nitrogen in a vacuum oven to obtain a yield of 118.5 g of amorphous poly(p-phenylene sulfide/sulfone) having an inherent viscosity of 0.26, a T.sub. g of 205° C, and a PMT of 271° C.
In a run within the scope of this invention, 65.2 g (60 percent assay, 0.5 mole) sodium sulfide, 0.2 g sodium hydroxide (to react with sodium bisulfide and sodium thiosulfate present in trace amounts in the sodium sulfide), 51.0 g (0.5 mole) lithium acetate dihydrate, and 158.3 g N-methyl-2-pyrrolidone were charged to a stirred 1-liter autoclave, which was then flushed with nitrogen. Dehydration of the mixture by heating to 205° C yielded 41 ml of distillate containing 33.0 g water. To the residual mixture were charged 143.6 g (0.5 mole) bis(p-chlorophenyl) sulfone (melting point, 146°-147° C) and 40 g N-methyl-2-pyrrolidone. The resulting mixture was heated for 5 hours at 200° C at a pressure of 25-40 psig. The reaction product was washed repeatedly with hot water and dried at 80° C under nitrogen in a vacuum oven to obtain a yield of 118.8 g of amorphous poly(p-phenylene sulfide/sulfone) having an inherent viscosity of 0.40, a Tg of 215° C, and a PMT of 271° C.
Thus, based on inherent viscosity, the poly(p-phenylene sulfide/sulfone) produced in this Example was of much higher molecular weight than that produced in Example I, in which lithium acetate dihydrate was not employed.
Samples of the poly(p-phenylene sulfide/sulfone) produced in this Example were compression molded at a temperature of 290° C. Properties of the molded specimens are shown in Table I.
TABLE I ______________________________________ Density, g/cc.sup.(a) 1.4000 Flexural Modulus, psi × 10.sup.-.sup.3(b) 383 Tensile Break, psi.sup.(c) 11,970 Elongation, %.sup.(c) 8 Izod Impact Strength, ft-lb/in notch.sup.(d) 0.48 Heat Deflection Temperature, ° C at 264 psi.sup.(e) 184 Hardness, Shore D.sup.(f) 86 ______________________________________ .sup.(a) ASTM D 1505-68. .sup.(b) ASTM D 790-70. .sup.(c) ASTM D 638-68. .sup.(d) ASTM D 256-70. .sup.(e) ASTM D 648-56. .sup.(f) ASTM D 2240-68.
As shown in Table I, the poly(p-phenylene sulfide/sulfone) exhibited a good balance of properties, the heat deflection temperature being particularly outstanding.
In a control run outside the scope of this invention, without the use of a dehydration step as employed in Example I and with bis(p-chlorophenyl) sulfone from a different supplier, 65.2 g (60 percent assay, 0.5 mole) sodium sulfide, 0.2 g sodium hydroxide (to react with sodium bisulfide and sodium thiosulfate present in trace amounts in the sodium sulfide), 198.3 g N-methyl-2-pyrrolidone, and 143.6 g (0.5 mole) bis(p-chlorophenyl) sulfone (melting point, 146°-148° C) were charged to a stirred 1-liter autoclave, which was then flushed with nitrogen. The resulting mixture was heated for 5 hours at 200° C at a pressure of 45-55 psig. The reaction product was washed repeatedly with hot water and dried at 80° C under nitrogen in a vacuum oven to obtain a yield of 109.5 g of amorphous poly(p-phenylene sulfide/sulfone) having an inherent viscosity of 0.36, a Tg of 209° C, and a PMT of 275° C.
In a run within the scope of this invention, without the use of a dehydration step as employed in Example II and using bis(p-chlorophenyl) sulfone from the supplier which provided the sulfone employed in Example III, 65.2 g (60 percent assay, 0.5 mole) sodium sulfide, 0.2 g sodium hydroxide (to react with sodium bisulfide and sodium thiosulfate present in trace amounts in the sodium sulfide), 51.0 g (0.5 mole) lithium acetate dihydrate, 198.3 g N-methyl-2-pyrrolidone, and 143.6 g (0.5 mole) bis(p-chlorophenyl) sulfone (melting point, 146°-148° C) were charged to a stirred 1-liter autoclave, which was then flushed with nitrogen. The resulting mixture was heated for 5 hours at 200° C at a pressure of 65-75 psig. The reaction product was washed repeatedly with hot water and dried at 80° C under nitrogen in a vacuum oven to obtain a yield of 116.9 g of amorphous poly(p-phenylene sulfide/sulfone) having an inherent viscosity of 0.52, a T.sub. g of 210° C, and a PMT of 275° C.
Thus, based on inherent viscosity, the poly(p-phenylene sulfide/sulfone) produced in this Example was of much higher molecular weight than that produced in Example III, in which lithium acetate dihydrate was not employed.
In another control run outside the scope of this invention, employing a dehydration step as in Example I but with bis(p-chlorophenyl) sulfone from the supplier which provided the sulfone employed in Examples III and IV, 65.2 g (60 percent assay, 0.5 mole) sodium sulfide, 0.2 g sodium hydroxide (to react with sodium bisulfide and sodium thiosulfate present in trace amounts in the sodium sulfide), and 158.3 g N-methyl-2-pyrrolidone were charged to a stirred 1-liter autoclave, which was then flushed with nitrogen. Dehydration of the mixture by heating to 205° C yielded 16 ml of distillate containing 14.1 g water. To the residual mixture were charged 143.6 g (0.5 mole) bis(p-chlorophenyl) sulfone (melting point, 146°-148° C) and 40 g N-methyl-2-pyrrolidone. The resulting mixture was heated for 5 hours at 200° C at a pressure of 40-55 psig. The reaction product was washed repeatedly with hot water and dried at 80° C under nitrogen in a vacuum oven to obtain a yield of 121.9 g of amorphous poly(p-phenylene sulfide/sulfone) having an inherent viscosity of 0.29, a Tg of 203° C, and a PMT of 275° C.
In a run within the scope of this invention, using bis(p-chlorophenyl) sulfone from the supplier which provided the sulfone employed in Example V, 65.2 g (60 percent assay, 0.5 mole) sodium sulfide, 0.2 g sodium hydroxide (to react with sodium bisulfide and sodium thiosulfate present in trace amounts in the sodium sulfide), 64.02 g (0.5 mole) lithium benzoate, and 158.3 g N-methyl-2-pyrrolidone were charged to a stirred 1-liter autoclave, which was then flushed with nitrogen. Dehydration of the mixture by heating to 205° C yielded 18 ml of distillate containing 12.4 g water. To the residual mixture were charged 143.6 g (0.5 mole) bis(p-chorophenyl) sulfone (melting point, 146°-148° C) and 40 g N-methyl-2pyrrolidone. The resulting mixture was heated for 5 hours at 200° C at a pressure of 30-45 psig. The reaction product was washed repeatedly with hot water and dried at 80° C under nitrogen in a vacuum oven to obtain a yield of about 118 g of amorphous poly(p-phenylene sulfide/sulfone) having an inherent viscosity of 0.51, a Tg of 211° C, and a PMT of 275° C.
Thus, based on inherent viscosity, the poly(p-phenylene sulfide/sulfone) produced in this Example was of much higher molecular weight than that produced in Example V, in which lithium benzoate was not employed.
In a run within the scope of this invention, using a bis(p-chlorophenyl) sulfone: sodium sulfide mole ratio of 1.01:1, 65.2 g (60 percent assay, 0.5 mole) sodium sulfide, 0.2 g sodium hydroxide (to react with sodium bisulfide and sodium thiosulfate present in trace amounts in the sodium sulfide), 51.0 g (0.5 mole) lithium acetate dihydrate, and 158.3 g N-methyl-2-pyrrolidone were charged to a stirrer-equipped 1-liter autoclave, which was then flushed with nitrogen. Dehydration of the mixture by heating to 205° C yielded 39 ml of distillate containing 31.9 g water. To the residual mixture were charged 145.04 g (0.505 mole) bis(p-chlorophenyl) sulfone (melting point, 146°-148° C) and 40 g N-methyl-2-pyrrolidone. The resulting mixture was heated for 5 hours at 200° C at a pressure of 40-60 psig. The reaction product was washed repeatedly with hot water and dried at 80° C under nitrogen in a vacuum oven to obtain a yield of 122.2 g of amorphous poly(p-phenylene sulfide/sulfone) having an inherent viscosity of 0.37, a Tg of 209° C, and a PMT of 275° C. The melt flow of this polymer, determined by the method of ASTM D 1238-70, modified to a temperature of 316° C using a 5-kg weight, was 8 g/10 min.
In another run within the scope of this invention, conducted essentially as the preceding run except that 143.6 g (0.5 mole) of bis(p-chlorophenyl) sulfone instead of 145.04 g was used, there was obtained 123.0 g of amorphous poly(p-phenylene sulfide/sulfone) having an inherent viscosity of 0.48, a Tg of 219° C, and a PMT of 275° C. The melt flow of this polymer, determined as above, was only 1.6 g/10 min.
Thus, the poly(p-phenylene sulfide/sulfone) of higher melt flow prepared through use of bis(p-chlorophenyl) sulfone and sodium sulfide in a mole ratio of 1.01:1, respectively, was superior to the polymer obtained when the bis(p-chlorophenyl) sulfone and sodium sulfide were used in equimolar amounts for employment in applications such as injection molding where good melt processability is desired.
A run was conducted in which beneficial effects of washing the poly(p-phenylene sulfide/sulfone) at relatively high temperatures were demonstrated.
To a stirrer-equipped 1-liter autoclave were charged 65.2 g (60 percent assay, 0.5 mole) sodium sulfide, 0.2 g sodium hydroxide (to react with sodium bisulfide and sodium thiosulfate present in trace amounts in the sodium sulfide), 51.0 g (0.5 mole) lithium acetate dihydrate, 198.3 g N-methyl-2-pyrrolidone, and 143.6 g (0.5 mole) bis(p-chlorophenyl) sulfone (melting point, 146°-148° C). After the autoclave was flushed with nitrogen, the mixture was heated for 5 hours at 200° C at a pressure of 65-80 psig. The cooled reaction product was washed eight times with hot (approximately 80° C) water. A minor portion of this washed product was dried at 80° C under nitrogen in a vacuum oven to obtain 17.4 g of amorphous poly(p-phenylene sulfide/sulfone) (Polymer A). The remainder of the washed product was subjected to further washing by stirring in an autoclave with 400 ml water at 200° C for 1 hour. The mixture was cooled and filtered, and the polymer was again washed by stirring in an autoclave with 400 ml water at 200° C for 1 hour. The mixture was then cooled and filtered, and the polymer was washed four times with hot (approximately 80° C) water, then dried at 80° C under nitrogen in a vacuum oven to obtain 103.3 g of amorphous poly(p-phenylene sulfide/sulfone) (Polymer B). Properties of Polymer A and Polymer B are summarized in Table II.
TABLE II ______________________________________ Polymer A Polymer B ______________________________________ Inherent Viscosity 0.38 0.42 Tg, ° C 212 211 PMT, ° C 275 275 Ash, weight %.sup.a 0.44 0.06 Incremental Melt Flow, g.sup.b First Minute 0.44 0.40 Second Minute 0.20 0.38 Third Minute 0.10 0.35 Fourth Minute 0.07 0.30 Fifth Minute 0.04 0.26 Sixth Minute --.sup.c 0.23 Seventh Minute --.sup.c 0.19 Eighth Minute --.sup.c 0.15 ______________________________________ .sup.a Determined by burning a sample in a crucible over an open flame, followed by further heating of the sample in a furnace at 1000° F (538+ C) for 4 hours. .sup.b Determined by the method of ASTM D 1238-70, modified to a temperature of 316° C using a 5-kg weight, except that the weight in grams was determined for each one-minute interval during a period of 5-8 minutes. .sup.c Not determined.
As shown in Table II, Polymer B, which had been washed with water at 200° C, gave a much lower value for ash than did Polymer A, which was washed only at the lower temperature. Also, Polymer B exhibited much greater melt flow stability under conditions of the melt flow test, a characteristic desirable in melt processing operations such as injection molding.
Small discs were compression molded at 295° C from Polymer A and Polymer B. The disc from Polymer A was dark brown and opaque whereas that from Polymer B was amber and clear. Thus, Polymer B was lighter in color and of greater clarity.
Claims (17)
1. A process for the production of high molecular weight aromatic sulfide/sulfone polymers which comprises contacting
a. at least one dihalo aromatic sulfone represented by the formula ##STR6## where each X is selected from the group consisting of fluorine, chlorine, bromine, and iodine; Z is a divalent radical selected from the group consisting of ##STR7## n is 0 or 1; A is selected from the group consisting of oxygen, sulfur, sulfonyl, and CR2 ; and each R is selected from the group consisting of hydrogen and alkyl radicals having 1 to about 4 carbon atoms, the total number of carbon atoms in all of the R groups in the molecule being 0 to about 12,
b. at least one alkali metal sulfide selected from the group consisting of sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide,
c. at least one alkali metal carboxylate represented by the formula R'CO2 M wherein R' is a hydrocarbyl radical and M is an alkali metal, and
d. at least one organic amide, under polymerization conditions including an elevated temperature, a period of time, and proportions of reactants sufficient to cause the reactants to react with each other and from an aromatic sulfide/sulfone polymer having recurring ##STR8## units, where each R, Z, and n is as defined above.
2. A process according to claim 1 wherein
c. is an alkali metal carboxylate wherein R' is a hydrocarbyl radical having from 1 to about 20 carbon atoms, and
d. is a cyclic or acyclic amide having from 1 to about 10 carbon atoms per molecule.
3. A process according to claim 1 wherein (a) can be represented by the formula ##STR9## where each X is selected from the group consisting of fluorine, chlorine, bromine, and iodine, and each R is selected from the group consisting of hydrogen and alkyl radicals having 1 to about 4 carbon atoms, the total number of carbon atoms in each molecule being within the range of 12 to about 24,
c. can be represented by the formula R'CO2 M wherein R' is a hydrocarbyl radical having from 1 to about 20 carbon atoms and M is an alkali metal, and
d. is a cyclic or acyclic amide having from 1 to about 10 carbon atoms per molecule.
4. A process according to claim 1 wherein the temperature of the reaction is in the range of about 170° C to about 240° C under sufficient pressure to maintain liquid phase conditions and further wherein the mole ratio of (a) to (b) is in the range of 0.9:1 to 2:1, the mole ratio of (c) to (b) is in the range of 0.05:1 to 4:1, and the amount of (d) present is 100 grams to 2500 grams per gram mole of (b).
5. A process according to claim 1 wherein
a. is bis(p-chlorophenyl) sulfone,
b. is sodium sulfide,
c. is lithium acetate dihydrate or lithium benzoate, and
d. is N-methyl-2-pyrrolidone.
6. A process for the production of high molecular weight aromatic sulfide/sulfone polymers which comprises:
1. forming a mixture comprising:
a. at least one alkali metal sulfide selected from the group consisting of sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide,
b. at least one alkali metal carboxylate represented by the formula R'CO2 M wherein R' is a hydrocarbyl radical and M is an alkali metal, and
c. at least one organic amide,
2. heating the mixture formed in (1) to an elevated temperature and for a period of time sufficient to effect dehydration of said mixture, and
3. adding
d. at least one dihalo aromatic sulfone represented by the formula ##STR10## wherein each X is selected from the group consisting of fluorine, chlorine, bromine, and iodine; Z is a divalent radical selected from the group consisting of ##STR11## each n is 0 or 1: A is selected from the group consisting of oxygen, sulfur, sulfonyl, and CR2 ; and each R is selected from the group consisting of hydrogen and alkyl radicals having 1 to about 4 carbon atoms, the total number of carbon atoms in all of the R groups in the molecule being 0 to about 12, to the heated mixture of (1) and subjecting the mixture thus formed to polymerization conditions including an elevated temperature, a period of time, and proportions of reactants sufficient to cause the reactants to react with each other and form an aromatic sulfide/sulfone polymer having recurring ##STR12## units, where each R, Z, and n is as defined above.
7. A process according to claim 6 wherein the heating of (2) is carried out under conditions such that the mixture is substantially dehydrated before addition of the dihalo aromatic sulfone and the mixture is cooled prior to addition of (d).
8. A process according to claim 6 wherein
b. is an alkali metal carboxylate wherein R' is a hydrocarbyl radical having from 1 to about 20 carbon atoms, and
c. is a cyclic or acyclic amide having from 1 to about 10 carbon atoms per molecule.
9. A process according to claim 6 wherein (d) can be represented by the formula ##STR13## where each X is selected from the group consisting of fluorine, chlorine, bromine, and iodine, and each R is selected from the group consisting of hydrogen and alkyl radicals having 1 to about 4 carbon atoms, the total number of carbon atoms in each molecule being within the range of 12 to about 24,
b. can be represented by the formula R'CO2 M wherein R' is a hydrocarbyl radical having from 1 to about 20 carbon atoms and M is an alkali metal, and
c. is a cyclic or acyclic amide having from 1 to about 10 carbon atoms per molecule.
10. a process according to claim 6 wherein the temperature of the reaction is in the range of about 170° C to about 240° C under sufficient pressure to maintain liquid phase conditions and further wherein the mole ratio of (d) to (a) is in the range of 0.9:1 to 2:1, the mole ratio of (b) to (a) is in the range of 0.05:1 to 4:1 and the amount of (c) present is 100 grams to 2500 grams per gram mole of (a).
11. A process according to claim 6 wherein
a. is sodium sulfide,
b. is lithium acetate dihydrate or lithium benzoate,
c. is N-methyl-2-pyrrolidone, and
d. is bis(p-chlorophenyl) sulfone.
12. A process according to claim 1 wherein the temperature of the reaction is in the range of about 170° C. to about 240° C. and under sufficient pressure to maintain liquid phase condition and further wherein the mole ratio of (a) to (b) is 1:1 to 1.03:1 to produce an aromatic sulfide/sulfone polymer exhibiting good melt processability.
13. A process according to claim 6 wherein the temperature of the reaction is in the range of about 170° C. to about 240° C. and under sufficient pressure to maintain liquid phase conditions and further wherein the mole ratio of (a) to (b) is 1:1 to 1.03:1 to produce an aromatic sulfide/sulfone polymer exhibiting good melt processability.
14. A process according to claim 13 wherein
a. is bis(p-chlorophenyl) sulfone,
b. is sodium sulfide,
c. is lithium acetate dihydrate, and
d. is N-methyl-2-pyrrolidone.
15. A process according to claim 1 wherein the polymer produced is separated from the reaction mass and then washed with water, at least a portion of the washing being conducted at a temperature of 130°-250° C., for a period of time sufficient to yield a polymeric product exhibiting low ash values and high melt flow stability.
16. A process according to claim 15 wherein
a. is bis(p-chlorophenyl) sulfone,
b. is sodium sulfide,
c. is lithium acetate dihydrate, and
d. is N-methyl-2-pyrrolidone.
17. A process according to claim 6 wherein the polymer produced is separated from the reaction mass and then washed with water, at least a portion of the washing being conducted at a temperature of 130°-250° C., for a period of time sufficient to yield a polymeric product exhibiting low ash values and high melt flow stability.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/616,094 US4016145A (en) | 1974-08-08 | 1975-09-23 | Production of aromatic sulfide/sulfone polymers |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US495450A US3919177A (en) | 1973-11-19 | 1974-08-08 | P-phenylene sulfide polymers |
US05/616,094 US4016145A (en) | 1974-08-08 | 1975-09-23 | Production of aromatic sulfide/sulfone polymers |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US495450A Continuation-In-Part US3919177A (en) | 1973-11-19 | 1974-08-08 | P-phenylene sulfide polymers |
Publications (1)
Publication Number | Publication Date |
---|---|
US4016145A true US4016145A (en) | 1977-04-05 |
Family
ID=27051764
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/616,094 Expired - Lifetime US4016145A (en) | 1974-08-08 | 1975-09-23 | Production of aromatic sulfide/sulfone polymers |
Country Status (1)
Country | Link |
---|---|
US (1) | US4016145A (en) |
Cited By (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4102875A (en) * | 1976-06-22 | 1978-07-25 | Phillips Petroleum Company | Aromatic sulfide/sulfone polymer production |
US4125525A (en) * | 1976-06-22 | 1978-11-14 | Phillips Petroleum Company | Aromatic sulfide/sulfone polymer production |
US4127713A (en) * | 1977-11-14 | 1978-11-28 | Phillips Petroleum Company | Aromatic sulfide/sulfone polymer production |
EP0033906A1 (en) * | 1980-01-29 | 1981-08-19 | Phillips Petroleum Company | Process for the production of aromatic sulfide/sulfone polymers |
EP0193755A1 (en) * | 1985-03-05 | 1986-09-10 | Hüls Aktiengesellschaft | Homo- and copolymers of poly(arylene sulphides) having keto and ether groups and process for their preparation |
EP0266755A2 (en) * | 1986-11-05 | 1988-05-11 | Phillips Petroleum Company | Polyarylene sulfide sulfone prepreg |
EP0301566A2 (en) * | 1987-07-31 | 1989-02-01 | Phillips Petroleum Company | Aromatic sulfide/sulfone polymer production |
US4808694A (en) * | 1988-03-14 | 1989-02-28 | Phillips Petroleum Company | Poly(arylene sulfide sulfone) polymer containing ether groups |
EP0309954A1 (en) * | 1987-09-30 | 1989-04-05 | Phillips Petroleum Company | Production of aromatic sulfide/sulfone polymers |
EP0325061A2 (en) * | 1987-12-24 | 1989-07-26 | Tosoh Corporation | Process for producing poly (para-phenylene-sulfide) |
EP0348189A2 (en) * | 1988-06-23 | 1989-12-27 | Tosoh Corporation | Production of poly (arylene sulfide sulfone) |
US4988796A (en) * | 1990-02-20 | 1991-01-29 | Phillips Petroleum Company | Process for preparing poly(arylene sulfide sulfone) |
US5008368A (en) * | 1989-08-03 | 1991-04-16 | Phillips Petroleum Company | Preparation of poly(arylene sulfide/sulfone) polymer with addition of water after polymerization is initiated |
US5013822A (en) * | 1989-12-07 | 1991-05-07 | Phillips Petroleum Company | Process for preparing poly(arylene sulfide sulfone) with in-situ preparation of alkali metal carboxylate |
US5015702A (en) * | 1989-10-06 | 1991-05-14 | Phillips Petroleum Company | Treatment of poly(arylene sulfide/sulfone) polymers |
US5015725A (en) * | 1987-09-29 | 1991-05-14 | Phillips Petroleum Company | Aromatic sulfide/sulfone polymer production |
US5024876A (en) * | 1990-02-28 | 1991-06-18 | Phillips Petroleum Company | Reinforced plastic comprising poly(arylene sulfide sulfone) polymer containing ether groups matrix |
US5041532A (en) * | 1990-04-23 | 1991-08-20 | Phillips Petroleum Company | Method of treating a poly(arylene sulfide/sulfone) resin, and composition of matter made in accordance therewith |
US5045367A (en) * | 1990-02-28 | 1991-09-03 | Phillips Petroleum Company | Reinforced plastic comprising fibrous reinforcement treated with poly(arylene sulfide sulfone) polymer containing ether groups |
US5053486A (en) * | 1989-11-06 | 1991-10-01 | Phillips Petroleum Company | Process for preparing poly(arylene sulfide sulfone) with controlled ratio of alkali metal carboxylate to sulfur source |
US5057592A (en) * | 1990-02-28 | 1991-10-15 | Phillips Petroleum Company | Poly(arylene sulfide sulfone) polymer containing ether groups |
US5086163A (en) * | 1987-09-29 | 1992-02-04 | Phillips Petroleum Company | Aromatic sulfide/sulfone polymer production |
US5110902A (en) * | 1987-09-29 | 1992-05-05 | Phillips Petroleum Company | Aromatic sulfide/sulfone polymer production with complex of alkali metal hydrosulfide and alkali metal amino alkanoate |
US5134224A (en) * | 1991-02-14 | 1992-07-28 | Phillips Petroleum Company | Aromatic sulfide/sulfone polymer production |
US5138019A (en) * | 1990-02-28 | 1992-08-11 | Phillips Petroleum Company | Poly(arylene sulfide sulfone) polymer containing ether groups |
US5147719A (en) * | 1989-05-24 | 1992-09-15 | Phillips Petroleum Company | Production of phenylene sulfide-arylene sulfide/sulfone block copolymers |
US5235034A (en) * | 1989-11-06 | 1993-08-10 | Phillips Petroleum Company | Treatment of polyarylene sulfide/sulfone polymers with zinc compound and acidic solution |
US5245000A (en) * | 1991-07-01 | 1993-09-14 | Phillips Petroleum Company | Poly(arylene sulfide) polymer containing sulfone, ether and biphenyl groups |
USRE34464E (en) * | 1988-03-14 | 1993-11-30 | Phillips Petroleum Company | Poly(arylene sulfide sulfone)polymer containing ether groups |
US5266674A (en) * | 1990-12-24 | 1993-11-30 | Phillips Petroleum Company | Process for preparing arylene sulfide copolymers |
US5350834A (en) * | 1989-11-06 | 1994-09-27 | Phillips Petroleum Company | Treatment of polyarylene sulfide/sulfone polymers |
WO1995033682A1 (en) * | 1994-06-07 | 1995-12-14 | Hoechst Aktiengesellschaft | Process and filter for producing no2-free nitrogen monoxide with sulphurous polymers |
US5945490A (en) * | 1996-04-02 | 1999-08-31 | Tonen Chemical Corporation | Polyarylene sulfide and a composition thereof |
US6600009B2 (en) | 1996-10-31 | 2003-07-29 | Dainippon Ink And Chemicals, Incorporated | Process for the preparation of polyarylene sulfide |
US20080113187A1 (en) * | 2005-02-03 | 2008-05-15 | Kaoru Toyouchi | Resin Composition For High-Frequency Electronic And Electric Parts And Shaped Article Thereof |
US20090081462A1 (en) * | 2006-02-27 | 2009-03-26 | Asahi Kasei Chemicals Corporation | Long fiber filler reinforced resin pellet |
US20110124825A1 (en) * | 2008-07-22 | 2011-05-26 | Akihiro Konno | Production Process of Poly(Arylene Sulfide) Whose Content of Terminal Halogen Group Has Been Reduced |
US20110178268A1 (en) * | 2008-07-31 | 2011-07-21 | Kenji Suzuki | Production Process of Granular Poly(Arylene Sulfide) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3819582A (en) * | 1971-11-29 | 1974-06-25 | Ici Ltd | Polysulphones |
US3919177A (en) * | 1973-11-19 | 1975-11-11 | Phillips Petroleum Co | P-phenylene sulfide polymers |
-
1975
- 1975-09-23 US US05/616,094 patent/US4016145A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3819582A (en) * | 1971-11-29 | 1974-06-25 | Ici Ltd | Polysulphones |
US3919177A (en) * | 1973-11-19 | 1975-11-11 | Phillips Petroleum Co | P-phenylene sulfide polymers |
Cited By (52)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4102875A (en) * | 1976-06-22 | 1978-07-25 | Phillips Petroleum Company | Aromatic sulfide/sulfone polymer production |
US4125525A (en) * | 1976-06-22 | 1978-11-14 | Phillips Petroleum Company | Aromatic sulfide/sulfone polymer production |
US4127713A (en) * | 1977-11-14 | 1978-11-28 | Phillips Petroleum Company | Aromatic sulfide/sulfone polymer production |
EP0033906A1 (en) * | 1980-01-29 | 1981-08-19 | Phillips Petroleum Company | Process for the production of aromatic sulfide/sulfone polymers |
US4301274A (en) * | 1980-01-29 | 1981-11-17 | Phillips Petroleum Company | Aromatic sulfide/sulfone polymer production |
EP0033906B1 (en) * | 1980-01-29 | 1985-05-15 | Phillips Petroleum Company | Process for the production of aromatic sulfide/sulfone polymers |
EP0193755A1 (en) * | 1985-03-05 | 1986-09-10 | Hüls Aktiengesellschaft | Homo- and copolymers of poly(arylene sulphides) having keto and ether groups and process for their preparation |
EP0266755A2 (en) * | 1986-11-05 | 1988-05-11 | Phillips Petroleum Company | Polyarylene sulfide sulfone prepreg |
EP0266755A3 (en) * | 1986-11-05 | 1989-06-14 | Phillips Petroleum Company | Polyarylene sulfide sulfone prepreg |
AU607945B2 (en) * | 1986-11-05 | 1991-03-21 | Phillips Petroleum Company | Fiber-reinforced composite materials ("prepregs") useful for forming laminates |
US4958004A (en) * | 1987-07-31 | 1990-09-18 | Phillips Petroleum Company | Aromatic sulfide/sulfone polymer production |
EP0301566A3 (en) * | 1987-07-31 | 1989-03-15 | Phillips Petroleum Company | Aromatic sulfide/sulfone polymer production |
EP0301566A2 (en) * | 1987-07-31 | 1989-02-01 | Phillips Petroleum Company | Aromatic sulfide/sulfone polymer production |
US5110902A (en) * | 1987-09-29 | 1992-05-05 | Phillips Petroleum Company | Aromatic sulfide/sulfone polymer production with complex of alkali metal hydrosulfide and alkali metal amino alkanoate |
US5015725A (en) * | 1987-09-29 | 1991-05-14 | Phillips Petroleum Company | Aromatic sulfide/sulfone polymer production |
US5086163A (en) * | 1987-09-29 | 1992-02-04 | Phillips Petroleum Company | Aromatic sulfide/sulfone polymer production |
EP0309954A1 (en) * | 1987-09-30 | 1989-04-05 | Phillips Petroleum Company | Production of aromatic sulfide/sulfone polymers |
EP0325061A2 (en) * | 1987-12-24 | 1989-07-26 | Tosoh Corporation | Process for producing poly (para-phenylene-sulfide) |
EP0325061B1 (en) * | 1987-12-24 | 1995-12-06 | Tosoh Corporation | Process for producing poly (para-phenylene-sulfide) |
EP0336145A1 (en) * | 1988-03-14 | 1989-10-11 | Phillips Petroleum Company | Poly(Arylene sulfide sulfone) polymer containing ether groups |
USRE34464E (en) * | 1988-03-14 | 1993-11-30 | Phillips Petroleum Company | Poly(arylene sulfide sulfone)polymer containing ether groups |
US4808694A (en) * | 1988-03-14 | 1989-02-28 | Phillips Petroleum Company | Poly(arylene sulfide sulfone) polymer containing ether groups |
EP0348189A3 (en) * | 1988-06-23 | 1990-06-13 | Tosoh Corporation | Production of poly (arylene sulfide sulfone) |
EP0348189A2 (en) * | 1988-06-23 | 1989-12-27 | Tosoh Corporation | Production of poly (arylene sulfide sulfone) |
US5093467A (en) * | 1988-06-23 | 1992-03-03 | Tosoh Corporation | Production of poly(arylene sulfide sulfone) with excess water to alkali metal sulfide |
US5147719A (en) * | 1989-05-24 | 1992-09-15 | Phillips Petroleum Company | Production of phenylene sulfide-arylene sulfide/sulfone block copolymers |
US5008368A (en) * | 1989-08-03 | 1991-04-16 | Phillips Petroleum Company | Preparation of poly(arylene sulfide/sulfone) polymer with addition of water after polymerization is initiated |
US5015702A (en) * | 1989-10-06 | 1991-05-14 | Phillips Petroleum Company | Treatment of poly(arylene sulfide/sulfone) polymers |
US5350834A (en) * | 1989-11-06 | 1994-09-27 | Phillips Petroleum Company | Treatment of polyarylene sulfide/sulfone polymers |
US5053486A (en) * | 1989-11-06 | 1991-10-01 | Phillips Petroleum Company | Process for preparing poly(arylene sulfide sulfone) with controlled ratio of alkali metal carboxylate to sulfur source |
US5235034A (en) * | 1989-11-06 | 1993-08-10 | Phillips Petroleum Company | Treatment of polyarylene sulfide/sulfone polymers with zinc compound and acidic solution |
US5013822A (en) * | 1989-12-07 | 1991-05-07 | Phillips Petroleum Company | Process for preparing poly(arylene sulfide sulfone) with in-situ preparation of alkali metal carboxylate |
US4988796A (en) * | 1990-02-20 | 1991-01-29 | Phillips Petroleum Company | Process for preparing poly(arylene sulfide sulfone) |
US5024876A (en) * | 1990-02-28 | 1991-06-18 | Phillips Petroleum Company | Reinforced plastic comprising poly(arylene sulfide sulfone) polymer containing ether groups matrix |
US5045367A (en) * | 1990-02-28 | 1991-09-03 | Phillips Petroleum Company | Reinforced plastic comprising fibrous reinforcement treated with poly(arylene sulfide sulfone) polymer containing ether groups |
US5138019A (en) * | 1990-02-28 | 1992-08-11 | Phillips Petroleum Company | Poly(arylene sulfide sulfone) polymer containing ether groups |
US5057592A (en) * | 1990-02-28 | 1991-10-15 | Phillips Petroleum Company | Poly(arylene sulfide sulfone) polymer containing ether groups |
US5041532A (en) * | 1990-04-23 | 1991-08-20 | Phillips Petroleum Company | Method of treating a poly(arylene sulfide/sulfone) resin, and composition of matter made in accordance therewith |
US5266674A (en) * | 1990-12-24 | 1993-11-30 | Phillips Petroleum Company | Process for preparing arylene sulfide copolymers |
US5134224A (en) * | 1991-02-14 | 1992-07-28 | Phillips Petroleum Company | Aromatic sulfide/sulfone polymer production |
US5245000A (en) * | 1991-07-01 | 1993-09-14 | Phillips Petroleum Company | Poly(arylene sulfide) polymer containing sulfone, ether and biphenyl groups |
WO1995033682A1 (en) * | 1994-06-07 | 1995-12-14 | Hoechst Aktiengesellschaft | Process and filter for producing no2-free nitrogen monoxide with sulphurous polymers |
US5945490A (en) * | 1996-04-02 | 1999-08-31 | Tonen Chemical Corporation | Polyarylene sulfide and a composition thereof |
US6600009B2 (en) | 1996-10-31 | 2003-07-29 | Dainippon Ink And Chemicals, Incorporated | Process for the preparation of polyarylene sulfide |
US20080113187A1 (en) * | 2005-02-03 | 2008-05-15 | Kaoru Toyouchi | Resin Composition For High-Frequency Electronic And Electric Parts And Shaped Article Thereof |
US20090081462A1 (en) * | 2006-02-27 | 2009-03-26 | Asahi Kasei Chemicals Corporation | Long fiber filler reinforced resin pellet |
US20090176923A1 (en) * | 2006-02-27 | 2009-07-09 | Asahi Kasei Chemicals Corporation | Glass-fiber reinforced thermoplastic resin composition and molded article thereof |
US8993670B2 (en) | 2006-02-27 | 2015-03-31 | Asahi Kasei Chemicals Corporation | Glass-fiber reinforced thermoplastic resin composition and molded article thereof |
US20110124825A1 (en) * | 2008-07-22 | 2011-05-26 | Akihiro Konno | Production Process of Poly(Arylene Sulfide) Whose Content of Terminal Halogen Group Has Been Reduced |
US8680230B2 (en) | 2008-07-22 | 2014-03-25 | Kureha Corporation | Production process of poly(arylene sulfide) whose content of terminal halogen group has been reduced |
US20110178268A1 (en) * | 2008-07-31 | 2011-07-21 | Kenji Suzuki | Production Process of Granular Poly(Arylene Sulfide) |
US8609790B2 (en) | 2008-07-31 | 2013-12-17 | Kureha Corporation | Production process of granular poly(arylene sulfide) |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4016145A (en) | Production of aromatic sulfide/sulfone polymers | |
US4038259A (en) | Production of p-phenylene sulfide polymers | |
EP0033906B1 (en) | Process for the production of aromatic sulfide/sulfone polymers | |
US4127713A (en) | Aromatic sulfide/sulfone polymer production | |
CA1087347A (en) | Production of branched arylene sulfide polymers | |
US4039518A (en) | Production of p-phenylene sulfide polymers | |
US4038260A (en) | Production of p-phenylene sulfide polymers | |
US4038263A (en) | Production of p-phenylene sulfide polymers | |
US4102875A (en) | Aromatic sulfide/sulfone polymer production | |
US4096132A (en) | Production of p-phenylene sulfide polymers | |
US4116947A (en) | Branched arylene sulfide polymer production | |
US4089847A (en) | Temperature programming in the production of arylene sulfide polymers | |
CA1311084C (en) | Production of aromatic sulfide/sulfone polymers | |
US4125525A (en) | Aromatic sulfide/sulfone polymer production | |
US5008368A (en) | Preparation of poly(arylene sulfide/sulfone) polymer with addition of water after polymerization is initiated | |
CA1306575C (en) | Production of aromatic sulfide/ketone polymers | |
US5328980A (en) | Method of preparing poly(arylene sulfide) polymers, polymers and polymer blends | |
US5015702A (en) | Treatment of poly(arylene sulfide/sulfone) polymers | |
US5134224A (en) | Aromatic sulfide/sulfone polymer production | |
US5053486A (en) | Process for preparing poly(arylene sulfide sulfone) with controlled ratio of alkali metal carboxylate to sulfur source | |
US3876591A (en) | Arylene sulfide polymers | |
US4024118A (en) | P-Phenylene sulfide polymers | |
US3940375A (en) | Arylene sulfide polymers | |
US4070349A (en) | Aromatic sulfide/sulfone polymer production | |
US4958004A (en) | Aromatic sulfide/sulfone polymer production |